Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C255/00—Carboxylic acid nitriles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
  • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
  • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B57/00—Other synthetic dyes of known constitution
  • C09B57/02—Coumarine dyes

Definitions

• the present invention relates to a new class of luminous pigments, a process for their manufacture, their use in colouring organic materials, especially the use of such pigments as are sparingly soluble in water as disperse dyestuffs for dyestuffs for dyeing and printing hydrophobic fibres, their use as organic dye lasers and as industrial products and the material dyed or printed with new pigments.
• the new, fluorescent pigments which have been found, are N-substituted iminocoumarin derivatives of the general formula I ##STR2## wherein X 1 is a cyano group, a carboxamido group or an aryl or a heteroaryl radical, linked directly or through --CO or SO 2 group,
• X 2 is an amino group, hydroxy group or an alkoxy group, and when it is an amino group, may carry an optionally substituted alkylene or alkylidene group bound in ortho position to the nitrogen atom and in para position to the coumarin oxygen atom,
• X 3 is a hydrogen atom, a halogen atom or a cyano group
• X 4 is a functionally converted carboxyl group.
• the carboxamido group X 1 is a group --CONHR wherein R is a hydrogen atom, an optionally substituted lower alkyl group, especially those substituted by hydroxy or acyloxy group, a cycloalkyl group, an aryl or a heteroaryl group.
• radicals or groups refer to those radicals or groups containing not more than 6 carbon atoms.
• the aryl radicals are especially phenyl or naphthyl radicals optionally substituted by groups such as nitro or optionally substituted amino, halogen atoms e.g. fluorine, chlorine and bromine, or lower alkyl such as methyl, ethyl, n-propyl, isopropyl or n-or iso butyl radicals, or lower alkoxy, e.g. methoxy and ethoxy radicals.
• groups such as nitro or optionally substituted amino, halogen atoms e.g. fluorine, chlorine and bromine, or lower alkyl such as methyl, ethyl, n-propyl, isopropyl or n-or iso butyl radicals, or lower alkoxy, e.g. methoxy and ethoxy radicals.
• the heteroaryl radicals may be mono or bicyclic heteroaryl radicals e.g. pyridyl, thienyl, furyl, triazolyl, benzimidazolyl, benzoxazolyl, benzthiazolyl, quinoxalinyl or quinazolyl radicals.
• Such radicals may also carry substituents such as lower alkyl, lower alkoxy radicals or halogen atoms.
• the radical X 2 representing an amino group may also represent a mono or preferably disubstituted amino group.
• the substituents of the amino group are aliphatic hydrocarbon radicals especially lower alkyl radicals which may be optionally substituted for example by hydroxyl or nitrile groups, lower alkoxy groups with preferably 1 to 4 carbon atoms, acyloxy groups, phenoxy groups or halogen, such as chlorine or bromine.
• the nitrogen atom of the amino group may form part of a heteroring conjointly with the substituents present.
• the ring is preferably 5-membered or 6-membered and not aromatic; it can be, for example, the pyrrolidine or piperidine ring, and if this ring includes a further hetero-atom, for example, the morpholine radical or a piperazine ring which is optionally N'-substituted, especially by alkyl or acyl groups, such as the N'-acetylpiperazine radical, or a radical of the formula ##STR5##
• the group X 4 is preferably a carboxylic ester group especially ester of a lower alkanol such as methanol, ethanol or propanol, or a cyano group.
• the iminocoumarins which are to be used in accordance with the invention can be obtained by the known procedure of Knoevenagel condensation between salicylaldehydes of formula IV and active methylene compounds of the formula V ##STR7## where X 1 and X 2 have the meanings given earlier.
• Reaction between the iminocoumarins and the ethylene derivatives may be carried out in suitable organic solvents in the temperature range of room-temp. to 150°.
• solvents examples include hydrocarbons, such as benzene, toluene or xylenes, halogenated hydrocarbons, such as carbon tetrachloride, sym-tetrachloroethane, chlorobenzene or o-dichlorobenzene, or nitrohydrocarbons, such as nitromethane or nitrobenzene, ethers such as tetrahydrofuran, dioxane, dibutylether, esters, amides, nitriles such as ethyl acetate, dimethylformamide, acetonitrile or even dimethylsulfoxide can be used as solvent.
• hydrocarbons such as benzene, toluene or xylenes
• halogenated hydrocarbons such as carbon tetrachloride, sym-tetrachloroethane, chlorobenzene or o-dichlorobenzene
• a suitable solvent such as chlorobenzene or tetrahydrofuran
• the new pigments usually crystallize out of the reaction mixture on cooling and are easily isolated by filtration or are isolated by the removal of the solvent if necessary by steam distillation. If need be, they can be further purified by crystallization from high boiling organic solvents, such as dimethylformamide, chlorobenzene or o-dichlorobenzene.
• organic solvents such as acetone, alcohol, chlorobenzene, dimethylformamide and ethyl acetate exhibit strong fluorescence in daylight and in ultraviolet light.
• the new water-insoluble or sparingly soluble pigments are particularly suitable for dyeing textile material such as for example, acrylic or acrylo nitrile fibres, polyacrylonitrile fibres and copolymers of acrylonitrile and other vinyl compounds, such as acrylic esters, arylamides, vinylpyridine, vinyl chloride or vinylidene chloride, copolymers of dicyanoethylene and vinyl acetate, and of acrylonitrile block copolymers, fibres composed of polyurethanes, polyolefines, such as polypropylene modified by a base, polypropylene modified with nickel or unmodified polypropylene, cellulose triacetate and cellulose 21/2-acetate and particularly fibres composed of polyamides, such as nylon 6, nylon 6,6 or nylon 12, and of aromatic polyesters, such as those of terephthalic acid and ethylene glycol or 1,4-dimethylcyclohexane, and isophthalic acid and ethylene glycol.
• the new dyestuffs which are free from sulpho and quaternised nitrogen atoms are particularly suitable for dyeing textile material consisting of high molecular organic esters, such as cellulose 21/2-acetate or cellulose triacetate, but particularly for dyeing or printing textile material of polymeric esters of aromatic polycarboxylic acids with polyhydric alcohols, above all polyethylene glycol terephthalate or polycyclohexanedimethylol terephthalate or textured polyesters fibres such as, for examples, DIOLEN LOFT R (Ve occidentale Glazstoff-Werke), CRIMPLENE R (ICI), and SCHAPIRA R (Hoechst).
• DIOLEN LOFT R Ve occidentale Glazstoff-Werke
• CRIMPLENE R CRIMPLENE R
• SCHAPIRA R Hoechst
• the dyestuffs can, however, also be used for dyeing synthetic polyamide fibres, such as polyhexamethylene adipamide, polycaprolactam or polyamino undecanoic acid, and for dyeing polyolefines, especially polypropylene fibres. They belong to the class of the disperse dyestuffs, such as are defined, for example, in the Colour Index.
• compositions are suitable for bulk dyeing or pigmenting lacquers, oils and waxes and cellulose derivatives, especially cellulose esters, such as cellulose acetate.
• the new dyestuffs can be used also for laser applications.
• dispersing agents of the non-ionic group which can be used with advantage: addition products of 8 mols of ethylene oxide to 1 of p-tert. -octylphenol, of 15 or 16 mols of ethylene oxide to castor oil, and of 20 mols of ethylene oxide to the alcohol C 16 H 33 OH, ethylene oxide addition products with di-phenylethyl-phenols, polyethylene oxide tert.-dodecylthioethers, polyamide polyglycol ethers or addition products of 15 or 30 mols of ethylene oxide to 1 mol of the amine C 12 H 25 NH 2 or C 18 H 37 NH 2 .
• anionic dispersing agents may be mentioned: sulphuric acid esters of alcoholic of the aliphatic series with 8 to 20 carbon atoms, of the ethylene oxide adducts of the corresponding fatty acid amides, or of alkylated phenols with 8 to 12 carbon atoms in the alkyl radical; sulphonic acid esters having alkyl radicals with 8 to 20 carbon atoms; sulphation products of unsaturated fats and oils; phosphoric acid esters having alkyl radicals with 8 to 20 carbon atoms; fatty acid soaps and also alkylarylsulphonates, condensation products of formaldehyde with naphthalenesulphonic acid and ligninsulphonates.
• Suitable cationic dispersing agents are quaternary ammonium compounds containing alkyl or aralkyl radicals with 8 to 20 carbon atoms.
• the dyestuff preparations can also contain organic solvents, especially solvents which boil above 100° C. and which are preferably miscible with water, such as monoalkyl glycol ethers and dialkyl glycol ethers, dioxane, dimethylformamide or dimethylacetamide, tetramethylenesulphone or dimethylsulphoxide.
• solvents which boil above 100° C. and which are preferably miscible with water, such as monoalkyl glycol ethers and dialkyl glycol ethers, dioxane, dimethylformamide or dimethylacetamide, tetramethylenesulphone or dimethylsulphoxide.
• Dyestuff, dispersing agent and solvent can advantageously be ground with one another.
• polyester fibres are dyed from an aqueous dispersion with the dyestuffs according to the invention which are sparingly soluble in water, according to processes which are customary for polyester materials.
• Polyesters of aromatic polycarboxylic acids with polyhydric alcohols are preferably dyed at temperatures of above 100° C. and under pressure.
• the dyeing can, however, also be carried out at the boiling point of the dye bath in the presence of dyestuff carriers, for example alkali metal phenylphenolates, polychlorobenzene compounds or similar auxiliaries, or can be carried out by the padding process and subsequent hot after-treatment, for example thermofixing at 180° to 210° C.
• Cellulose 21/2-acetate fibres are preferably dyed at temperatures of 80° to 85° C., while cellulose triacetate fibres and synthetic polyamide fibre material are dyed advantageously at the boiling point of the dye bath.
• cellulose triacetate fibres and synthetic polyamide fibre material are dyed advantageously at the boiling point of the dye bath.
• the dyeings obtained according to the present process can be subjected to an after-treatment, for example by heating with an aquous solution of a non-ionic detergent.
• the textile materials mentioned are also printed according to the customary methods, for example by printing the goods with the printing paste containing, in addition to the dyestuff and the dyeing accelerator, thickeners and customary additives, such as, for example, urea and subsequently fixing the dyestuff by steaming for 15 minutes at 100° to 130° C.
• the new iminocoumarin derivatives of the formula I which can be used as disperse dyestuffs are very well absorbed on the above-mentioned hydrophobic organic fibre material, particularly on polyethylene glycol terephthalate fibres and, on this fibre material, they yield pure, full, yellow, orange, red and bluish red dyeings with a high brilliance and fluorescence.
• the dyeings are very fast to washing, fulling, rubbing, perspiration, solvents, decatising, light and sublimation.
• the iminocoumarin derivative required for above procedure is prepared as follows:
• the imino-coumarin used in this Example is prepared as follows:
• the iminocoumarin used in this Example is prepared by a process similar to one described for the preparation of anilide of cyanoacetic acid in place of 15.7 parts of 2-cyanomethylbenzimidazole; it is obtained as greenish yellow crystals, m.p. 200°-204°.
• a solution of 12.8 parts of tetracyanoethylene in 150 parts of tetrahydrofuran is added gradually to a stirred mixture of 33.2 parts of 7-diethylamino-3-(2'-benzimidazolyl) iminocoumarin and 150 parts of tetrahydrofuran at room temperature.
• the yellow colour of the mixture thereby changes to violet brown and violet brown crystals with metallic luster soon begin to separate.
• the mixture is stirred at room temperature for one-half hour and the violet brown crystalline product, which corresponds to the structure ##STR14## is filtered, washed with small amount of tetrahydrofuran and dried.
• the resulting yellow-brown mixture containing the iminocoumarin derivative ##STR22## is treated with 12.2 parts of ethoxymethylene malodinitrile and the resulting deep red solution is simmered for 1-2 minutes.
• the dyestuff of the formula ##STR23## separates out as brick-red crystals; it is filtered, washed with petroleum ether and dried. It dyes polyester a brilliant, fluorescent orange shade.
• a mixture of 5.0 parts of the dyestuff of Example 6 and 25.0 parts of acetic anhydride is heated on boiling water bath for 1 hour and poured into 250 parts of cold water.
• the brick red precipitate of the dyestuff ##STR24## that separates on standing is filtered, washed and dried. It also dyes polyester, an attractive, fluorescent, orange shade.
• Chlorobenzene extract is then refluxed with 15.7 parts of 2-cyanomethyl benzimidazole, 0.3 part of piperidine for 15 minutes and the resulting solution containing the iminocoumarin derivative ##STR44## is treated with 12.2 parts of ethoxymethylenemalodinitrile and refluxed further for 5 minutes.
• the dyestuff of the structure ##STR45## separates out as deep red crystals; it gives bright red dyeings on nylon and polyester.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Coloring (AREA)
• Plural Heterocyclic Compounds (AREA)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=4287016

Family Applications (2)

Family Applications After (1)

Country Status (2)

Cited By (3)

Families Citing this family (6)

Citations (4)

• 1977
  • 1977-04-04 US US05/784,198 patent/US4153618A/en not_active Expired - Lifetime
  • 1977-04-20 DE DE19772717599 patent/DE2717599A1/de active Pending
• 1979
  • 1979-01-31 US US06/008,703 patent/US4299959A/en not_active Expired - Lifetime

Patent Citations (4)

Also Published As

Similar Documents

Legal Events